CN1410460A - Preparation method diesel pour point reducer - Google Patents
Preparation method diesel pour point reducer Download PDFInfo
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- CN1410460A CN1410460A CN 02143889 CN02143889A CN1410460A CN 1410460 A CN1410460 A CN 1410460A CN 02143889 CN02143889 CN 02143889 CN 02143889 A CN02143889 A CN 02143889A CN 1410460 A CN1410460 A CN 1410460A
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- vinyl acetate
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Abstract
A pour depressor for diesel oil is prepared from vinyl acetate, C4-8 alpha-olefine and excessive ethylene through reaction in a reactor containing cyclohexane at 70-120 deg.c and under 4-9 MPa under the action of the trigger composed of peroxide and azo compound to synthesize the tribasic copolymer of ethylene-vinyl acetate-alpha-olefine. Its advantages are low reaction pressure, high output rate and high effect.
Description
Technical field
The invention belongs to the preparation method of high-efficiency diesel pour inhibitor, more precisely, is a kind of preparation method of reducing cold filter point of diesel oil and condensation point, improving the diesel-dope of diesel oil at low-temperature flowability of being used to.
Background technology
Diesel pour inhibitor, claim diesel flow improver again, in refining of petroleum enterprise and transportation important application is arranged, it not only can improve the low temperature flowability of diesel oil, diesel oil can normally be used in low temperature environment, also to increasing output of diesel oil, saving kerosene, raising refinery's production handiness, increase refinery economic benefit, crucial meaning is arranged simultaneously.Application to diesel pour inhibitor has become the important means that each refinery increases economic efficiency, and low-molecular-weight ethylene-vinyl acetate copolymer then is the most a kind of diesel pour inhibitor of present domestic and international application.
Disclosing a kind of among the USP 3981850 is raw material with ethene and vinyl acetate between to for plastic, is solvent with benzene, is initiator with the ditertiary butyl peroxide, adopts the method for single still intermittence type polymerization prepared in reaction ethene-vinyl acetate type diesel pour inhibitor.This method is a solvent owing to having adopted the bigger benzene of toxicity, is unfavorable for environment protection, in addition, because the temperature of reaction height of this method causes energy consumption to increase.
Disclosing a kind of among the CN 91111489.0 is raw material with ethene and vinyl acetate between to for plastic, is solvent with the non-leaded gasoline, is initiator with the di-cyclohexylperoxy dicarbonate, adopts the method for single still intermittence type polymerization prepared in reaction ethene-vinyl acetate type diesel pour inhibitor.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of diesel pour inhibitor.
A kind of preparation method of diesel pour inhibitor, it is characterized in that with vinyl acetate between to for plastic, carbon number being α-positive alkene and excessive ethene of 4-8, the reactor that has stirring of hexanaphthene is equipped with in injection, under the initiator effect of forming by peralcohol and azo-compound, in 70 ℃-120 ℃, 4.0MPa-9.0MPa under the pressure, synthetic molecular-weight average is 1000-2000, ester content is ethene-vinyl acetate-alpha-olefin terpolymer of 25-35wt%.
The mass ratio of vinyl acetate between to for plastic of the present invention, alpha-olefin, composite initiator and hexanaphthene is 1: 0.01-0.05: 0.05-0.10: 2.0-3.0.
Initiator of the present invention is the mixture of benzoyl peroxide and 2,2'-Azobis(2,4-dimethylvaleronitrile), and the mass ratio of the two is 1: 0.05-0.95.
The alpha-olefin that the present invention is used, preferably 1-hexene.
The present invention is owing to adopt ethene-vinyl acetate-alpha-olefin terpolymer to substitute ethene-vinyl acetate copolymer of the prior art, makes it compared with prior art have more good cold filter clogging temperature and/or the pour point depression point performance of falling; Owing to adopted composite initiator, reduced temperature of reaction, thereby reduced energy consumption.
The present invention has compared with the prior art that reaction pressure is low, once through yield is high, save energy, technology is simple and characteristics such as the cold filter clogging temperature effect is obvious fall in product.
Embodiment
The present invention is further described below by embodiment, and its raw material source and specification see Table 1 among the embodiment.
Embodiment 1:
In having 10 liters of reactors of stirring, drop into 1050 gram hexanaphthenes.After vacuumizing with vacuum pump, charge into ethylene gas to 0.2MPa, then emptying; Triplicate like this.Stir, be warming up to 85 ℃ and constant temperature, in still, charge into ethene simultaneously to 6.0MPa and remain this pressure.With volume pump with 3100 gram vinyl acetate between to for plastics, 1-hexenes, composite initiator and hexanaphthene by 1: 0.02: 0.10: the mixed of 2.0 (quality) is prepared liquid uniformly and is carried out polyreaction with the input speed injection reactor of 40 ml/min.Here, composite initiator is composited by benzoyl peroxide and the 2,2'-Azobis(2,4-dimethylvaleronitrile) ratio in 1: 0.3 (quality).Charging finishes, and continues reaction 15 minutes, and reaction mass amounts to reaction 110 minutes in still.The material of emitting is placed still kettle, steam and remove reaction solvent and unreacted monomer, residuum is described terpolymer-diesel pour inhibitor and does agent A.Reaction result is listed in table 2.
Get the above-mentioned dried agent of 0.6 gram, 0.2 gram C-9 heavy aromatics and 0.2 gram kerosene are made high-efficiency diesel pour inhibitor A, join in the 2000 gram diesel oil, and the method for pressing SH/T 0248-92 is measured the cold filter clogging temperature of diesel oil, investigates its result of use.It the results are shown in Table 3.
Embodiment 2:
In having 10 liters of reactors of stirring, drop into the industrial hexanaphthene of 1050 grams.After vacuumizing with vacuum pump, charge into ethylene gas to 0.2MPa, then emptying; Triplicate like this.Stir, be warming up to 100 ℃ and constant temperature, in still, charge into ethene simultaneously to 6.0MPa and remain this pressure.With volume pump with 3100 gram vinyl acetate between to for plastics, 1-hexenes, composite initiator, hexanaphthene by 1: 0.02: 0.10: the mixed of 2.0 (quality) is prepared liquid uniformly and is carried out polyreaction with the input speed injection reactor of 45 ml/min.Here, composite initiator is composited by benzoyl peroxide and the 2,2'-Azobis(2,4-dimethylvaleronitrile) ratio in 1: 0.3 (quality).Charging finishes, and continues reaction 15 minutes.Reaction mass amounts to reaction 100 minutes in still.The material of emitting is moved in the still kettle, steam and remove reaction solvent and unreacted monomer, residuum is described terpolymer-diesel pour inhibitor and does agent B.Reaction result is listed in table 2.
Get the above-mentioned dried agent of 0.6 gram, 0.2 gram C-9 heavy aromatics and 0.2 gram kerosene are made high-efficiency diesel pour inhibitor B, join in the 2000 gram diesel oil, and the method for pressing SH/T 0248-92 is measured the cold filter clogging temperature of diesel oil, investigates its result of use.It the results are shown in Table 3.
Embodiment 3:
In having 10 liters of reactors of stirring, drop into the industrial hexanaphthene of 1050 grams.After vacuumizing with vacuum pump, charge into ethylene gas to 0.2MPa, then emptying; Triplicate like this.Stir, be warming up to 80 ℃ and constant temperature, in still, charge into ethene simultaneously to 5.5MPa and remain this pressure.With volume pump with 3100 gram vinyl acetate between to for plastics, 1-hexenes, composite initiator, hexanaphthene by 1: 0.02: 0.08: the mixed of 2.0 (quality) is prepared liquid uniformly and is carried out polyreaction with the input speed injection reactor of 40 ml/min.Here, composite initiator is composited by benzoyl peroxide and the 2,2'-Azobis(2,4-dimethylvaleronitrile) ratio in 1: 1 (quality).Charging finishes, and continues reaction 15 minutes.Reaction mass amounts to reaction 110 minutes in still.The material of emitting is moved in the still kettle, steam and remove reaction solvent and unreacted monomer, residuum is described terpolymer-diesel pour inhibitor and does agent C.Reaction result is listed in table 2.
Get above-mentioned dried agent 0.6 gram, 0.2 gram C-9 heavy aromatics and 0.2 gram kerosene are made high-efficiency diesel pour inhibitor C, join in the 2000 gram diesel oil, and the method for pressing SH/T 0248-92 is measured the cold filter clogging temperature of diesel oil, investigates its result of use.It the results are shown in Table 3.Embodiment 4:
In having 10 liters of reactors of stirring, drop into the industrial hexanaphthene of 1050 grams.After vacuumizing with vacuum pump, charge into ethylene gas to 0.2MPa, then emptying; Triplicate like this.Stir, be warming up to 90 ℃ and constant temperature, in still, charge into ethene simultaneously to 6.5MPa and remain this pressure.With volume pump with 3100 gram vinyl acetate between to for plastics, 1-hexenes, composite initiator, hexanaphthene by 1: 0.02: 0.08: the mixed of 2.0 (quality) is prepared liquid uniformly and is carried out polyreaction with the input speed injection reactor of 45 ml/min.Here, composite initiator is composited by benzoyl peroxide and the 2,2'-Azobis(2,4-dimethylvaleronitrile) ratio in 1: 1 (quality).Charging finishes, and continues reaction 15 minutes.Reaction mass amounts to reaction 100 minutes in still.The material of emitting is moved in the still kettle, steam and remove reaction solvent and unreacted monomer, residuum is described terpolymer-diesel pour inhibitor and does agent D.Reaction result is listed in table 2.
Get above-mentioned dried agent 0.6 gram, 0.2 gram C-9 heavy aromatics and 0.2 gram kerosene are made high-efficiency diesel pour inhibitor D, join in the 2000 gram diesel oil, and the method for pressing SH/T 0248-92 is measured the cold filter clogging temperature of diesel oil, investigates its result of use.It the results are shown in Table 3.
Table 1
Sequence number name of an article specification purposes
1 ethene purity＞99.4% polymerization single polymerization monomer
2 vinyl acetate between to for plastic purity＞99.0% polymerization single polymerization monomer
3 1-hexene chemical pure polymerization single polymerization monomers
4 peroxidation benzene first industrial goods initiators
5 azos two industrial goods initiator in different heptan
6 cyclohexane purity＞99.5% solvent
7 C-9 heavy aromatics thinners
8 kerosene thinners
Table 2
Sequence number polymer output/gram molecular-weight average
1.Ester content/%wt
2.
1 A 1700 1660 31.6
2 B 1970 1454 28.8
3 C 2027 1600 31.6
4 D 1,873 1,557 29.8 annotate: 1. the mensuration of molecular-weight average adopts vapour pressure osmometry (VPO method).
2. ester content is measured and is adopted saponification-volumetry: take by weighing 0.2 gram sample in Erlenmeyer flask
In, adding 20 milliliters of toluene and 5 ml concns is the KOH-second of 0.5 mol
Alcoholic solution refluxes after 2 hours, with the sulfuric acid titration of 0.05 mol.
Table 3
Cold filter clogging temperature/℃ diesel oil * pour point depressant adds dosage/%wt
Add add agent before the agent after
0# A 0.05 -3 -10
0# B 0.05 -3 -14
0# C 0.05 -3 -17
0# D 0.05 -3 -12
-20# A 0.05 -17 -33
-20# B 0.05 -17 -29
-20# C 0.05 -17 -29
-20# D 0.05 -17 -36
* used diesel oil is Dushanzi refinery product.
Claims (4)
1. the preparation method of a diesel pour inhibitor, it is characterized in that with vinyl acetate between to for plastic, carbon number being alpha-olefin and the excessive ethene of 4-8, the reactor that has stirring of hexanaphthene is equipped with in injection, under the initiator effect of forming by peralcohol and azo-compound, in 70 ℃-120 ℃, 4.0MPa-9.0MPa under the pressure, synthetic molecular-weight average is 1000-2000, ester content is ethene-vinyl acetate-alpha-olefin terpolymer of 25-35wt%.
2. in accordance with the method for claim 1, it is characterized in that vinyl acetate between to for plastic, carbon number are 1 for the mass ratio for the alpha-olefin of 4-8, composite initiator and hexanaphthene: 0.01-0.05: 0.05-0.10: 2.0-3.0.
3. in accordance with the method for claim 1, it is characterized in that initiator is the mixture of benzoyl peroxide and 2,2'-Azobis(2,4-dimethylvaleronitrile), the mass ratio of the two is 1: 0.05-0.95.
4. in accordance with the method for claim 1, it is characterized in that alpha-olefin is the 1-hexene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021438897A CN1172971C (en) | 2002-10-11 | 2002-10-11 | Preparation method diesel pour point reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021438897A CN1172971C (en) | 2002-10-11 | 2002-10-11 | Preparation method diesel pour point reducer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1410460A true CN1410460A (en) | 2003-04-16 |
| CN1172971C CN1172971C (en) | 2004-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021438897A Expired - Fee Related CN1172971C (en) | 2002-10-11 | 2002-10-11 | Preparation method diesel pour point reducer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322056A (en) * | 2021-08-02 | 2021-08-31 | 德仕能源科技集团股份有限公司 | High-efficiency pour point depressant for crude oil and preparation method and application thereof |
-
2002
- 2002-10-11 CN CNB021438897A patent/CN1172971C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322056A (en) * | 2021-08-02 | 2021-08-31 | 德仕能源科技集团股份有限公司 | High-efficiency pour point depressant for crude oil and preparation method and application thereof |
| CN113322056B (en) * | 2021-08-02 | 2021-11-23 | 德仕能源科技集团股份有限公司 | High-efficiency pour point depressant for crude oil and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1172971C (en) | 2004-10-27 |
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